This invention relates to a herbicidal composition having a rapid action, an improved effect and a long-term stability of preparation.
Among the light-induced herbicidal compositions represented by the general formula (I), the 3-substituted phenylpyrazole derivatives represented by the general formula (I-1) are known compounds disclosed in JP-A-3-163063 and JP-A-4-211065, wherein it is mentioned that these compounds have, as herbicides for foliage treatment, an outstanding herbicidal activity on the general broad-leaved weeds noxious in the upland farming.
It is known that a similar herbicidal activity is exhibited by a number of compounds resembling the general formula (I-1) in the over-all chemical structure and relative configuration of substituents used as light-induced or protox-inhibiting herbicides [Anderson et al., ACS Symposium Series, Vol. 559, Porphyric Pesticides, S. O. Duke and C. A. Robeiz eds., p.18-34 (1994)]. It is also known that a resistance to these light-induced herbicides can generally be given to plants by introducing a specific gene into the plants (International Patent Application WO98/29554).
On the other hand, organophosphorus herbicidal compounds such as the N-(phosphonomethyl)-glycine or salts thereof disclosed in JP-A-47-39538 and JP-A-57-95994, the 4-[hydroxy(methyl)phosphino]-DL-homoalanine or salts thereof disclosed in JP-A-57-26564 and the 4-[hydroxy(methyl)phosphino]-L-homoalany-L-alanyl-L-alanine or salts thereof disclosed in JP-A-50-23282, etc. are well known as non-selective herbicides for foliage treatment.
Further, JP-A-7-242510 discloses herbicidal compositions containing a 3-substituted phenylpyrazole derivative and an organophosphorus herbicidal compound.
Further, Weed Sci. Soc. 25, (1977), p.275-287 refers to the adjuvant effect of alcohol alkoxylates on N-(phosphonomethyl)glycine. However, this technique is insufficient in the adjuvant effect and the alcohol alkoxylates are not readily compatible with aqueous solution of N-(phosphonomethyl)glycine.
Thus, it has been demanded to improve the herbicidal effect and rapid action of a herbicidal composition containing a light-induced herbicidal compound (especially a 3-substituted phenylpyrazine derivative) and an organophosphorus herbicidal compound.
The present inventors have conducted extensive studies with the aim of solving the problems mentioned above to find that, by adding an ethylenediamine alkoxylate and an alcohol alkoxylate as surfactants to a herbicidal composition containing one or more compounds selected from light-induced herbicidal compounds, especially one or more compounds selected from the 3-substituted phenylpyrazole derivatives represented by the general formula (I-1), and organophosphorus herbicidal compounds as active ingredients, the rapid action of the composition can be made excellent and the effect of the composition can be improved by the synergistic action of the active ingredients and the surfactants, besides there can be obtained a herbicidal composition keeping stable for a long period of time. Based on this finding, this invention has been accomplished.
The present invention relates to a herbicidal composition containing one or more compounds selected from light-induced herbicidal compounds and one more compounds selected from organic herbicidal compounds as active ingredients; and containing an ethylenediamine alkoxylate and an alcohol alkoxylate as surfactants.
Particularly, the present invention relates to a herbicidal composition containing, as active ingredients, one or more compounds selected from the group consisting of the compounds represented by the following general formula (I):
wherein P represents P1 to P9: 
wherein X1, Y, Y1, Y2, R3, R4, R5 and R6 are as defined below, and Q represents Q1 to Q11: 
wherein R1 represents a (C1-C6) alkyl group; R2 represents a hydrogen atom, a (C1-C6) alkyl group or a halo (C1-C6) alkyl group; R3 represents a (C1-C6) alkyl group, a halo (C1-C6) alkyl group, a (C3-C6) cycloalkyl group, a (C2-C6) alkenyl group or a (C2-C6) alkynyl group; R4 represents a hydrogen atom or a (C1-C6) alkyl group; R5 represents a hydrogen atom, a (C1-C6) alkyl group, a halo (C1-C6) alkyl group, a (C2-C6) alkenyl group or a (C2-C6) alkynyl group; R6 represents a (C1-C6) alkyl group, a (C2-C6) alkenyl group or a (C2-C6) alkynyl group; X1 and X2 represent halogen atoms which may be the same or different; Y represents xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94 or xe2x80x94SO2xe2x80x94; Y1 represents xe2x80x94Oxe2x80x94 or xe2x80x94Sxe2x80x94; Y2 represents xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NHxe2x80x94; and n represents an integer of 0 to 1;
and more particularly, one or more compounds selected from the group consisting of the 3-substituted phenylpyrazole derivatives represented by the following general formula (I-1): 
wherein R represents xe2x80x94Y1xe2x80x94R3 (wherein R3 represents a (C1-C6) alkyl group, a halo (C1-C6) alkyl group, a (C2-C6) alkenyl group or a (C2-C6) alkynyl group; and Y1 represents xe2x80x94Oxe2x80x94 or xe2x80x94Sxe2x80x94), xe2x80x94Y2CH(R4)COxe2x80x94OR5 (wherein R4 represents a hydrogen atom or a (C1-C6) alkyl group; R5 represents a hydrogen atom, a (C1-C6) alkyl group, halo (C1-C6) alkyl group, a (C2-C6) alkenyl group or a (C2-C6) alkynyl group; and Y2 represents xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NHxe2x80x94), xe2x80x94COOCH(R4)COxe2x80x94Y1 R5 (wherein R4, R5 and Y1 are as defined above), or xe2x80x94COOR6 (wherein R6 represents a (C1-C6) alkyl group, a (C2-C6) alkenyl group or a (C2-C6) alkynyl group); R1 represents a (C1-C6) alkyl group; R2 represents a hydrogen atom, a (C1-C6) alkyl group or a halo (C1-C6) alkyl group; X1 and X2 represent halogen atoms which may be the same or different; Y represents xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94 or xe2x80x94SO2xe2x80x94; and n represents an integer of 0 to 1; and
one or more compounds selected from the group consisting of organophosphorus herbicidal compounds, and
further containing, as surfactants, an ethylenediamine alkoxylate and an alcohol alkoxylate.
Among the substituents in the general formula (I) and general formula (I-1), the term xe2x80x9c(C1-C6) alkyl groupxe2x80x9d means a straight or branched chain alkyl group having 1-6 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl and the like; xe2x80x9chalo (C1-C6) alkyl groupxe2x80x9d means a straight or branched chain alkyl group having 1-6 carbon atoms substituted with one or more halogen atoms which are selected from the group consisting of chlorine atom, fluorine atom, iodine atom and bromine atom and may be the same or different; xe2x80x9c(C2-C6) alkenyl groupxe2x80x9d means a straight or branched chain alkenyl group having 2-6 carbon atoms; and xe2x80x9c(C2-C6) alkynyl groupxe2x80x9d means a straight or branched chain alkynyl group having 2-6 carbon atoms.
As examples of the light-induced herbicidal compounds of this invention, the following ones can be referred to:
(1) 3-(4-Chloro-5-(cyclopentyloxy)-2-fluorophenyl)-5-isopropylidene-1,3-oxazolidindione (general name: pentoxazone)
(2) Pentyl [2-chloro-5-(cyclohexa-1-ene-1,2-dicarboximide)-4-fluorophenoxy]-acetate (general name: flumiclorac-pentyl)
(3) 7-Fluoro-6-[(3,4,5,6-tetrahydro)phthalimido]-4-(2-propynyl)-1,4-benzoxazin-3(2H)-one (general name: flumioxazin)
(4) Ethyl (RS)-2-chloro-3-[2-chloro-5-(4-fluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-4-fluorophenyl]propionate (general name: carfentrazone-ethyl)
(5) 2xe2x80x2,4xe2x80x2-Dichloro-5xe2x80x2-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-methane-sulfonanilide (general name: sulfentrazone)
(6) 2-(2,4-Dichloro-5-propyn-2-yloxyphenyl)-5,6,7,8-tetrahydro-1,2,4-triazolo[4,3-a]pyridin-3(2H)-one (general name: azafenidin)
(7) 5-tert-Butyl-3-[2,4-dichloro-5-(propyn-2-yloxy)phenyl]-1,3,4-oxadiazole (general name: oxadiargyl)
(8) 5-tert-Butyl-3-(2,4-dichloro-5-isopropoxy-phenyl)-1,3,4-oxadiazol-2(3H)-one (general name: oxadiazon)
(9) Methyl [2-chloro-4-fluoro-5-(5,6,7,8-tetrahydro-3-oxo-1H,3H-[1,3,4]thiadiazolo[3,4-a]pyriadzin-1-ylideneamino)phenylthio]acetate (general name: fluthacet-methyl) etc.
As the compound groups exhibiting a similar activity, the following diphenyl ether type compounds are known:
nitrofen (general name), bifenox (general name), oxyfluorfen (general name), acifluorfen (general name), fomesafen (general name), etc. Besides above, the following 3-substituted phenylpyrazole derivatives represented by the general formula (I-1) can also be referred to:
General Formula (I-1) 
Among the 3-substituted phenylpyrazole derivatives of the present invention represented by the general formula (I-1), preferred is the compound No. 19.
On the other hand, as the organophosphorus herbicidal compounds used in the present invention, the following can be referred to:
N-(phosphonomethyl)glycine or salts thereof, such as N-(phosphonomethyl)glycine isopropylamine salt (hereinafter, referred to as xe2x80x9cCompound Axe2x80x9d), or ammonium salt thereof or N-(phosphonomethyl)glycine trimethyl-sulfonium salt (hereinafter, referred to as xe2x80x9cCompound Bxe2x80x9d);
4-[hydroxy(methyl)phosphino]-DL-homoalanine or salts thereof such as 4-[hydroxy(methyl)phosphino]-DL-homoalanine ammonium salt (hereinafter, referred to as xe2x80x9cCompound Cxe2x80x9d);
4-[hydroxy(methyl)phosphino]-L-homoalanyl-L-alanyl-L-alanine or salts thereof, such as 4-[hydroxy-(methyl)phosphino]-L-homoalanyl-L-alanyl-L-alanine sodium salt (hereinafter, referred to as xe2x80x9cCompound Dxe2x80x9d); etc.
Among these organophosphorus herbicidal compounds, preferred is N-(phosphonomethyl)glycine isopropylamine salt.
As the ethylenediamine alkoxylates used as a surfactant in this invention, the compounds represented by the following general formula (II): 
wherein EO represents xe2x80x94Oxe2x80x94CH2CH2xe2x80x94, PO represents xe2x80x94Oxe2x80x94CH(CH3)CH2xe2x80x94, Exe2x80x2O represents xe2x80x94CH2CH2xe2x80x94Oxe2x80x94; Pxe2x80x2O represents xe2x80x94CH2(CH3)CHxe2x80x94Oxe2x80x94 and a, b, d, e, f, g, h, and i represent integers of 1to 20 which may be the same or different, can be referred to. As preferable examples thereof, Teric 170 (manufactured by Huntsman Co.) and Teric 173 (manufactured by the same company as above) can be referred to. One or more species of the above-mentioned ethylenediamine alkoxylates may be selected and put to use.
As the alcohol alkoxylates used in this invention, the compounds represented by the following general formula (III) can be referred to:
CkH2k+1xe2x80x94(EO)j(PO)lxe2x80x94OHxe2x80x83xe2x80x83(III)
wherein EO represents xe2x80x94Oxe2x80x94CH2CHxe2x80x94; PO represents xe2x80x94Oxe2x80x94CH(CH3)CH2xe2x80x94; and k and l represent an integer of 1 to 20 which may be the same or different. Preferable examples of such compounds include the following: Noigen ET-165 (manufactured by Daiichi Kogyo Seiyaku K.K.), Adekatol SO-135 (manufactured by Asahi Denka K.K.), Noigen ET-115 (manufactured by Daiichi Kogyo Seiyaku K.K.), NK (Newkalgen)-D-1107S (manufactured by Takemoto Yushi K.K.), Lutensol T08 (manufactured by BASF Co.), TO-347 (manufactured by Nippon Nyuukazai K.K.), etc. One or more species of such alcohol alkoxylates may be selected and put to use.
In the herbicidal composition of the present invention, compounding ratios of the ingredients are as follows. That is, in 100 parts by weight of the herbicidal composition, the light-induced herbicidal compound is used in an amount of 0.01-10.0 parts by weight and preferably 0.1-2.0 parts by weight; the organophosphorus herbicidal compound is used in an amount of 1.0-60.0 parts by weight and preferably 5.0-40.0 parts by weight; the ethylenediamine alkoxylate is used in an amount of 0.1-25 parts by weight and preferably 10-25 parts by weight; and the alcohol alkoxylate is used in an amount of 0.1-15.0 parts by weight and preferably 0.1-5.0 parts by weight.
When the herbicidal composition of the present invention is put to use, the composition is made into an appropriate preparation form in accordance with the purpose according to the conventional method in the pesticide preparation, and then put to use. For instance, the composition is blended with a solid carrier, a liquid carrier or other necessary adjuvants, and the blended mixture thus obtained is made into a preparation form such as a suspension concentrate in which the active ingredient exists in the state of suspended fine particles, or a wettable powder, or a water dispersible granule, or the like and then put to use.
Further, it is also possible, if desired, to blend the composition of the present invention with an emulsifier comprising the same surfactant as used in the present invention in an amount of 0.1-99.0 parts by weight and preferably 25.0-75.0 parts by weight per part by weight of the light-induced herbicide compound of general formula (I), and a commercially available preparation containing an organophosphorus compound as an active ingredient thereof, at the time of preparing a liquid preparation to be sprayed, and thereafter to put to use.
When using a suspension concentrate or a water dispersible granule which contains, as the active ingredients thereof, a finely pulverized material comprising 0.01-10 parts by weight of the light-induced herbicidal compound represented by the general formula (I) without surfactant, and 1-50 parts by weight of an organophosphorus herbicidal compound; it is also possible, if desired, to make the same surfactant as used in this invention into a solution elsewhere and to mix the resulting solution with the suspension concentrate or water dispersible granule of this invention at the time of preparing a liquid mixture to be sprayed, at a ratio of 10-90 parts by weight of the surfactant solution per part by weight of the light-induced herbicidal compound represented by the general formula (I).